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Publication numberUS3901868 A
Publication typeGrant
Publication dateAug 26, 1975
Filing dateSep 20, 1974
Priority dateSep 27, 1973
Also published asCA1040347A1, DE2445776A1, DE2445776B2, DE2445776C3
Publication numberUS 3901868 A, US 3901868A, US-A-3901868, US3901868 A, US3901868A
InventorsHideyuki Aikawa, Hisawaki Hamada, Hideo Ishikawa, Kyohei Oizumi, Haruo Ueno
Original AssigneeUbe Industries
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for producing butadiene polymers
US 3901868 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent n 1 Ueno et al.

[ Aug. 26, 1975 1 PROCESS FOR PRODUCING BUTADIENE POLYMERS [75] inventors: Haruo Ueno, Chiba; Kyohei Oizumi,

lchihara; Hldeo lshikawa, lchihara; Hisawaki Hamada,ichihara; Hideyuki Aikawa, lchihara. all of Japan [73] Assignce: Ube industries, Ltd., Japan [22] Filed: Sept. 20, 1974 [21] Appl. No.: 507,867

[30] Foreign Application Priority Data [56] References Cited UNITED STATES PATENTS 3.778.424 l2/l973 Shotaro Sugiura et al. 260/943 Primary Examiner-Joseph L. Schofer Assistant Examiner-F. R. Cervi [57] ABSTRACT A butadiene polymer consisting essentially of syndiotactic l.2-poiybutadiene is produced by the successive steps oi: (A) preparing; a catalyst component solution by dissolving, in an inert organic solvent containing l,3-butadienc, a cobalt compound, soluble in the organic solvent, such as (i) cobalt-B-diketone complex, (ii) cobalt-fi-keto acid ester complex, (iii) cobalt salt of organic carboxylic acid and (iv) halogenated cobalt-ligand compound-complex, and an organoaluminum commpound, (B) preparing a catalyst composition by mixing the catalyst component solution with an alcohol, ketonc or aldehyde compound and carbon disulfide; (C) providing a polymerization mixture containing desired amounts of 1,3-butadiene, the catalyst composition and an inert organic solvent, and (D) polymerizing l,3-butadiene at a temperature of 20 to 80C.

46 Claims, 2 Drawing Figures Pmminw z m 3.901.868

sum 1 or 2 (M00) (c=|oo) ORGANOAL NUM I 005 A COMPOUN cause of its disadvantages of low yield and the unsatisfactory physical properties of the polymer product.

In order to overcome the disadvantages of the abovementioned process. a polymerization catalyst comprising a cobalt compound. an organoaluminum and carbon disulfide has been proposed. The proposed polymerization catalyst can convert l.3-butadiene in an inert organic solvent to syndiotactic l.2-polybutadiene having a high melting point of approximately 200 to 215C and a high crystallinity. However. this process is unsatisfactory for industrial purposes because of the relatively low yield of the polymer product. Further. the process can not control the melting point of the polymer product. In order to eliminate these disadvantages. an improvement was proposed. In the improvement. l.3-butadiene is polymerized in an inert organic solvent in the presence of a catalyst consisting of a cobalt compound. an organoaluminum compound. carbon disulfide and a nitrile compound. One problem in this process is that the nitrile compound which is harmful to the human body is difficult to recover from the polymerization mixture.

The object of the' present invention is to provide a process for producing-butadienc polymers composed essentially of l.2-structure and having a desired melting point.

Another object ofthe present invention is to provide a process for producing butadiene polymers composed essentially of l.2-structure with a relatively high yield.

The above-mentioner' objects are accomplished by the process of the present invention which comprises the steps of:

A. preparing a catalyst component solution by dissolving in an inert organic solvent containing l.3- butadiene. (a) at least one cobalt compound selected from the group consisting of (i) B-diketone complexes of cobalt. (ii) /3-keto-aci d ester complexes of cobalt. (iii) cobalt salts of organic carboxylic acids having 6 to carbon atoms. and (iv) complexes of halogenated cobalt compounds of the formula CoXn, wherein X represents a halogen atom and n represents 2 or 3. with an organic'compound selected from the group consisting oftertiary amines. alcohols. tertiary phosphines. ketones and N.N-dialkyl-amides. and (b) at least one organoaluminum compound of the formula AlR wherein R represents a hydrocarbon radical of l to 6 carbon atoms.

B. preparing'a catalyst composition by mixing said catalyst component solution with (c) at least one organic compound selected from the group consisting of alcohol compounds having I to ZS carbon atoms. ke-' tone compounds having 3 to 20,carbon atoms and aldehyde compounds having I to carbon atoms and (d) carbon disulfidc.

2 C. providing a polymerization mixture containing desired amounts of l.3-butadiene. said catalyst composition and an inert organic solvent. and

D. polymerizing said lJ-butadiene in said polymerization mixture at a temperature of -20 to 80C.. The polymer produced by the process of the present invention is composed essentially of syndiotactic l.2- structure and has a melting point of 70 to 2 l 0C which depends on the composition of the catalyst. especially. the amount ofthe alcohol. ketone or aldehyde compounds uscd as a catalyst component. Also. the polymer produced by the process of the present invention can be used to form films. sheets. fibers and other shaped articles. and utilized for producing various graft copolymers by reacting graft monomers with the vinyl radicals in the butadiene polymer. Especially. since the high melting point of butadiene polymer produced by the process of the present invention is valuable for producing plastic shaped articles due to its high resistance to organic solvent. for example. n-hexane and benzene. The features and advantages of the process of the present invention are more fully described in the following detailed description and the accompanying drawings in which:

FIG. I shows the proportions of water. organoaluminum compound and coballt compound in the catalyst component solution. in a triangular coordinate system. and;

FIG. 2 shows an infrared absorption spectrum of a polymer product prepared by the process of the present invention.

In the first step in the process of the present invention. a catalyst component solution is prepared by dissolving at least one cobalt compound and at least one organoaluminum compound in an inert organic solvent containing l.3-butadiene dissolved therein.

The term "an inert organic solvent" used herein refers to an organic solvent chemically inert to all of the catalyst components used in the process of the present invention. l.3-butadiene and the butadiene polymer. The inert organic solvent may be selected from the group consisting of aromatic hydrocarbons. aliphatic hydrocarbons. alicyclic hydrocarbons. halogenated aromatic hydrocarbons. halogenated aliphatic hydrocarbons. halogenated alicycllc hydrocarbons. and mixtures of two or more of the above-mentioned com pounds. The aromatic hydrocarbons may be benzene. toluene. xylenes. ethyl benzene. diethyl benzene or isobutyl benzene; and aliphatic hydrocarbon may be nhexane. isohexanes, n-heptane. n-octane. isooctanes. n-decane, 2,2-dimethyl butane, petroleum ether. petroleum benzine. ligroine. kerosene. petroleum spirit or petroleum naphtha. and the alicyclic hydrocarbon may be either cyclohexane or methyl cyelohexane. The halogenated aromatic hydrocarbon may be ehlorobenzene. dichlorobenzenes. triichlorobenzenes or chlorotoluencs. and the halogenated aliphatic hydrocarbon may be methylene chloride. chloroform. tetrachloromethane, l.2-dichloroethane. l.l .ltrichloroethane. l.l .2-trichloroethane tetrachloroethanes. trichloropropanc. n-butyl chloride or n-amyl chloride.

The cobalt compound usable for the process of the present invention is soluble in an inert organic solvent selected from the group consisting of i. B-diketone complexes of cobalt.

ii. B-keto-acid ester complexes of cobalt.

iii. cobalt salts of organic earboxylic acid having 6 to carbon atoms. and iv. complexes of halogenated cobalt compounds of the formula: CoXn wherein X represents a halogen atom and n represents 2 or 3. with an organic compound selected from the group consisting of tertiary amines. alcohols. tertiary phosphines. ketones and N.N-dialkyl-amides.

The B-diketone compound to form a complex with a cobalt atom is of the formula:

wherein R and R. which are the same as or different from one another, are an alkyl radical of l to 6 carbon atoms and R and R". which are the same as or different from one another. are a hydrogen atom or an alkyl radical having I to 6 carbon atoms. Such type of B- diketone complex of cobalt may be cobalt (ll) acetylacetonate or cobalt (Ill) acetylacetonate.

The B-keto-acid ester to form a complex with a cobalt atom may be of the formula:

wherein R'. R. R and R are the same as defined above. Such type of the cobalt complex may be a cobalt-acetoacetic acid ethyl ester complex.

The cobalt salt of organic earboxylic acid may be either cobalt octoate or cobalt naphthenate.

in the ligand compounds capable of forming a complex with a halogenated cobalt compound, the tertiary amine may be pyridine. triethylamine, tributylamine or dimethylaniline. the alcohol may be methyl alcohol or kyl. cycloalltyl. or aryl radical of l to 6 carbon atoms. t

Preferably. the organo-aluminum compound-may be trimethylaluminum. triethylaluminum or triphenylalu minum.

In the preparation of. the catalyst component solution. it is important that the cobalt compound and the organo-aluminum compound are dissolved in the inert organic solvent containing l.3'butadiene. lfthe preparation is carried out in the absence of Lit-butadiene. the resultant catalyst component solution isnot effecti ve as a component of the catalyst composition of the present invention. The l.3-butadiene is preferably used in a ratio by mole of at least l.0. more prcferably.-at

a That is. ifthe l.3-butadiene is used in a large ratio. for

example. 1.000 to 200.000. by mole to the cobalt conipound. the activity of the catalyst composition is similar to that of the catalyst composition prepared from the catalyst component solution containing l.3- butadiene in a ratio of 10 200. by mole. lfthe ratio is less than l.0. the resultant catalyst composition has poor activity. in that the catalystcomposition cannot be used industrially. The catalyst component solution may contain either all or a portion of the amount of l.3-butadiene to be polymerized in the polymerization mixture. The catalyst component solution is preferably prepared at a temperature of l0 to 50C and preferably contains 0.0005 to 1.0% by mole. more preferably. 0.00] to 0.5% by mole. ofthe cobalt compound. 0.00l to I07: by mole. more preferably. 0.03 to 57: by mole. of the organoaluminum compound based on the amount by mole of l.3-butadiene to be polymerized. The ratio of the amount of mole of the organoaluminum compound to that of the cobalt compound is preferably in a range from 0.] to 500. more preferably. from 0.5 to I00.

It is well-known that the organoaluminum compound should be prevented from contact with water which may decompose the organoaluminum compound. Aecordingly. it is preferable that the inert organic solvent to be used to prepare the catalyst component solution is preliminarily dehydrated at least up to a content of water which is insufficient to completely decompose the entire amount of the organoaluminum compound.

In the preparation of the catalyst component solution. it is preferable that the cobalt compound is firstly dissolved in the inert organic solvent in the presence of l.3-butadiene and the organoaluminum compound is secondly dissolved in the above solution. However. if the catalyst component solution is prepared by firstly dissolving the organoaluminum compound in the inert organic solvent containing the l.3- butadiene and secondly dissolving the cobalt compound in the above-prepared solution. it is preferable that the proportion of the water. the organoaluminum compound and the cobalt compound is in the range detailed below. Provided that in the catalyst component solution. the water. the organoaluminum compound and the cobalt compound in a ratio by mole percentage of a:h:c., the proportion u. h. c is on orv within a figure defined. in a triangular coordinate system having three ordinates respectively presenting the mole percentages of the water. organoaluminum compound and cobalt compound. by coordinate A (a 49.8. b 50 and c 0.2). B (a =0. b=99.8 and i.-=0.2). C (n =0. h=25 and c=). D (a=20.h=2$ and c==55) and E (a= 20. b= 5S and c= 25).

FIG. I shows the above-mentioned figure ABCDli in the triangular coordinate system.

It is preferable that the' catalyst component solution be prepared using a dehydrated inert organic solvent. The inert organic solvent may contain therein either no water or at most 500 p.p.m.. preferably. at most 200 p.p.m. of water. if the content of water in the inert organic solvent is larger than 500 p.p.m.. the catalyst component solution has to contain a relatively large amount of the cobalt compound and organoaluminum compound. This results in an economic disadvantage.

In the process of the present invention. it is desirable that the catalyst component solution is maintained for at least 30 seconds. more preferably, at least I minute and. thereafter. subjected to the preparation ofthe catalyst composition.

In order to prepare a catalyst composition. the catalyst component solution is mixed with at least one organic compound selected from the group consisting of alcohol compound having l to 25 carbon atoms. ketone compounds having 3 to 20 carbon atoms and aldehyde compounds having I to 20 carbon atoms and carbon disulfide. The preparation of the catalyst composition is preferably carried out at a temperature of to 50C.

The above-mentioned alcohol compound usable for the present invention is selected from the group consisting of monohydric alcohols. polyhydric alcohols and polyhydric alcohol derivatives having at least one hydroxyl radical. which have 1 to 25 carbon atoms. The monohydric alcohol is selected from the group consisting of saturated aliphatic alcohols. unsaturated aliphatic alcohols, alicyclic alcohols. aromatic alcohols and heterocyclic alcohols.

The saturated aliphatic alcohol may-be methyl alcohol. ethyl alcohol. n-propyl alcohol, isopropyl alcohol. n-butyl alcohol. sec-butyl alcohol. tert-butyl alcohol. isobutyl alcohol. n-amyl alcohol. isoamyl alcohol. sceamyl alcohol. tcrt-amyl alcohol. n-hexyl alcohol. 2- ethylbutyl alcohol. n-heptyl alcohol, 2-heptyl alcohol. n-octyl alcohol. 2-oetyl alcohol. Z-cthylhexyl alcohol. capryl alcohol. nonyl alcohol. n-decyl alcohol. lauryl alcohol or 4-methylpentanol-2.

6 aromatic ketoncs. for example. :tcelophcnone, propiophenonc. butylophenone. valerophcnone, benzophenone. dibcnzyl kctone and .Z-aceto-haphthone, and her erocyclic ketones. for instance. 3-acctothienone and Z-acetofuron.

The aldehyde compound having 1 to carbon atoms usable for the present invention may be selected from the group consisting of aliphatic aldehydes. for example. formaldehyde. acetaldchyde. propionaldchyde. n-butyl aldehyde. isohutyl aldehyde. nvaleraldehydc. isovaleraldehyde. pivalic aldehyde. caproie aldehyde. heptnldchyde. cuprylic aldehyde. pclargon aldehyde. capric aldehyde. undccyl aldehyde.

laurie aldehyde. trideeyl aldehyde. mystic aldehyde.

The unsaturated aliphatic alcohol may be allyl acts-- hol. erotyl alcohol or propargyl alcohol. The alicyclic alcohol may be cyclopentanol. cyclohexanol. 2- methylcyclohexanol or a-terpineol. The aromatic alcohol may be benzyl alcohol. cinnamyl alcohol and triphenyl carbinol. The heterocyclic alcohol may be either furfuryl alcohol or tetrahydrofurfuryl alcohol.

The polyhydric alcohol usable for the present invention maybe selected from ethylene glycol. propylene glycol. .l.3-butane diol. l.5-pentanc diol. 1.6-hexaric diol. LIOdecane diol. ,glycerin. l.l.l.-trishydroxypropane. l.2.6-hexane 'triol. peritaerythritol and trimethylol propane.

The polyhydric alcohol derivative having at least one hydroxyl radical usable for the present invention may be selected from the group consistingofethylene glycol monoalkyl ether. diethylene glycol. 'diethylene glycol monoalkyl ether triethylene glycol. triethyleneglycol monoalkyl ether. propylene glycolrnon oalkyl ether and diacetone alcohol. In the above-mentioned derivatives. the monoalkyl groups may have I too carbon atoms.

The ketone compound having 3 to 20 carbon atoms usable for the present invention may be selectedfrom the group consisting of aliphatic ketones. for example. acetone. acetylacetonc. ethylmethyl kctone. methylpropylkctonc. isopropylmethyl hetonc. butylmethylketone. iso-butylmeth yl ketonei pinacolone. diethyl ketone. butyrone. di-isopropyl-ketone and di isobutyl ketone; alic ylic ketoncs. for example. cyck ibutanone. cyclopentanone. cyclohexanone and cyclododccanunc:

pentadecyl aldehyde. palmitic aldehyde and stearic aldehyde; aliphatic dialdchydcs. for example. glyoxal and succindialdehyde; aromatic aldehyde. for example. benzaldehyde. o. m and p-tolualdehydes. salicyl aldehyde. aand B- naphthoaldehydcs and o-. mand panisaldehydcs. and; heterocyclic aldehydes. for example. frufural.

The alcohol. ketone or aldehyde compound mentioned above is preferably used in a proportion of 0.5 to 500094. more preferably. 1 to 10007:. by mole. based on the amount by mole of l.3-butadiene to be polymerized in the polymerization mixture. The physical properties. particularly. the melting point. of the polymer product can be varied in response to the proportion of the alcohol. ketone or aldehyde compound in the polymerization mixture.

Also. it is preferable that the alcohol. kctone or aldehyde compound is used at a ratio by mole of 2 to 25.000. more preferably. l0 to 5.000. to the amount by mole of the organoaluminum compound in the catalyst composition.

The carbon disulfide is preferably contained in a proportion of 0.0005 2% by mole. more preferably. 0.001 to I)? by mole. based on the amount by mole of the l.3-butadiene to be polymerized in the polymerization mixture.

In the process of the present invention. the larger the proportion of the carbon disulfide in a range from about 0.0005 to about 0.5% by mole based on the amount by mole of the l.3 -butadiene to be polymerized in the polymerization mixture. the larger the yield of the polymer product obtained from the polymerization mixture. However. too large an amount ofcarbon disulfide. for example. larger than 0.5% by mole. causes a decrease of the polymer product yield. In the process of the present invention. an increase of the proportion of the amount of alcohol. ketone or aldehyde to that of l.3-butadiene to be polymerized in the'polymerization mixture causes a decrease of the melting point of the butadien c polymer. produced from the above polymerization mixture.

Also. in the range from about 0.5% to about 200% by mole of the alcohol. ketone or aldehyde compound based on the amount by mole of the l. 3-butadiene to be polymerized. the larger the proportion of the alcohol. ketone or aldehyde compound. the larger the polymer product yield. However. in the proportion larger than about 200% by mole. the larger the proportion of the alcohol. ketone or aldehyde compound. the lower the yield ofthc polymer product. Accordingly. it is pos; sible to obtain a polymer product having a desi e-J melting point between about to about 210C hy justing the proportion of the alcohol. ketone at aid.-

hyde compound based on the amount by.- mote of tin. i t

l.3-htttatliene to be polymerized in the polymerization mixture.

it is known that in the conventional process for producing butadiene polymer by polymerizing 1.3- butadiene in the presence ofa catalyst prepared from a cobalt compound and an organoaluminum compound. the addition of an alcohol ketone or aldehyde to the polymerization mixture results in deactivation of the catalyst. Accordingly, the alcohol ketone or aldehyde compound is utilized as a polymerization-stopper for the above-mentioned conventional process. However. in the process of the present invention. the alcohol. ketone or aldehyde does not act as the polymerization stopper. Sometimes, the addition ofthe alcohol. ketone or aldehyde can result in enhancement ofthe activity of the catalyst composition and, therefore, in an increase of polymer product yield. Further, it should be noted thatthe melting point of the polymer product can be controlled by adjusting the proportion of the alcohol, ketone or aldehyde compound to the l,3-butadiene in the polymerization mixture. Such effect of the alcohol, ketone or aldehyde compound in the process of the present invention can not be anticipated from the conventional methods.

in the preparation ofthe catalyst composition. the alcohol. ketone or aldehyde compound and the carbon disulfide to be mixed with'the catalyst component solution may contain either no or a small amount of water. in the case where the catalyst composition contains water, the total amount of water is preferably in a ratio by mole of 0.0l to 10000 to the amount by mole of the cobait compound in the catalyst composition.

in the process of the present invention, the polymerization mixture is prepared using the catalyst composition by any of the followingimethods. Method l l. A catalyst component solution is prepared by dissolving a portion of adesired amount of l,3-butadiene to be polymerized in an inert-organic solvent, and then, dissolving a cobalt compound and an organoaluminum compound in the above solutipn.

2. An alcohol, ketone or afdehyde compound and 2. A polymerization mixture is prepared by admixing an alcohol. ketone or aldehyde compound and carbon disulfide to the catalyst component solution.

If the catalyst compostion contains the entire amount of l.3-butadiene to be polymerized and the entire amount ofthc inert organic solvent to be present in the polymerization mixture. that is, in Method 3, the catalyst composition is used as the polymerization mixture without addition. However. when the catalyst composition contains only a portion of the desired amount of l,3-butadiene to be polymerized and a portion of the desired amount of the inert organic solvent to be present in the polymerization mixture, the necessary amounts of the l.3-butadiene and the inert organic solvent are mixed with the catalyst composition to prepare the polymerization mixture. The l,3-butadiene to be polymerized is preferably in an amount of 2 to 30% based on the weight of the inert organic solvent in the polymerization mixture. The type of the additional inert organic solvent to be added to the polymerization mixture may be either the same as or different from that in the catalyst component solution. Usually. the additional inert organic solvent is preferably the same as the inert organic solvent in the catalyst component solution.

The polymerization of l.3-butadiene is carried out at a temperature of 20 to 80C. preferably. 5 to C. The polymerization may be effected either under 21 normal pressure or a pressurized pressure.

The polymer product produced by the process of the present invention is composed essentially, that is. 80% by weight or more, of sindiotactic l,2-structure. Referring to FIG. 2, the infrared absorption spectrum of a polymer product of the present invention has a remarkcarbon disulfide are mixed with the catalyst component solution to prepare a catalyst composition.

3. The balance of the desired amount of 1,3- butadiene is dissolved in an inert organic solvent and the solution is' mixed to the catalyst composition to pre pare a polymerization mixtu in which the desired amount of l,3-butadicne to polymerized is contained.

Method 2 r l. A catalyst component soluf-bn is prepared by dissolving a portion of a desired ati'yount of l,3-butadiene to be polymerized in an inert otganic solvent and further dissolving a cobalt compound and an organoaluminum compound in the above sd tion..

2. in order to prepare a poly rization mixture, the catalyst component solution, an lcohol ketoneor aldehyde compound and carbon di lfideare admixed in an optional order. to a solution 0* he balance ofthe desired amount of l,3-butadiene in aninert organic solvent.

Method 3 y I l. in order to prepare a catalyst Jmponcnt solution. the entire amount of 1.3-butadien to be polymerized is dissolved in an inert organic solv and a cobalt compound and an organoaluminum ompound are dissolved in the solution.

able absorption at 660 cm. The absorption is characteristic to syndiotactic l,2-structure. As stated hereinbefore, the process of the present invention can produce the polymer product having a desired melting point by varying the concentration of the alcohol, ketone or aldehyde compound in the catalyst composition. Generally, the lower the melting point ofthc polymer product, the higher the solubility of the polymer product in an organic solvent, for example, hot benzene. For example, the polymer. product having a melting point of 189C has a small solubility of less than l0% in hot benzene of C. Compared with this, another polymer product having a melting point of 155C can be completely dissolved in hot benzene at 80C.

Various embodiments of the process of the present invention in practice are illustrated by the following working-examples. These examples are intended merely to illustrate the present invention and not in any sense to limit the scope in'which the present invention can be practiced.

in the following examples, the content of l,2- structure in the polymer product was determined by the measurement of nuclear magnetic resonance (NMR) using a normal method, the melting point of the polymer product was indicated by a peak temperature of a heat absorption curve drawn by a differential scanning calorimeter (DSC), and the reduced specific viscosity of the polymer product was measured in a tetrahydronaphthalene solution containing the 0.15 g/IOO ml of the polymer productat a temperature of C, and indicated in the unit of 'nsp/C.

in each example. a polymerization mixture was prepared by the following operations.

A glass separable flask having a capacity of 2000 ml was subjected to the replacement of its inside atmospheric air by nitrogen gas and. then. received 760 ml of dehydrated benzene containing l.0 millimole of water and 74 g of l.3-butadiene dissolved therein. The benzene solution was mixed with l millimole of cobalt octoate which was in the state of a benzene solution containing 0.l millimoles/ml of the cobalt octoate. One minute after the above mixing. 2 millimoles of trlcthylaluminum in the state of a benzene solution containing l millimole/ml of the triethylaluminum was added to the mixture and the mixture was stirred for l minute to prepare a catalyst, component solution. Thereafter, methyl alcohol in an amount indicated in Table l was added to the catalyst component solution and l minute after the above addition, 0.6 millimoles of carbon disulfide. in the state of a benzene solution containing 0.3 millimoles/ml of the carbon disulfide. was mixed with the mixture. The resultant polymerization mixture was stirred at a temperature of30C for 60 minutes to polymerize the l.3-butadiene.

in order to separate and precipitate the polymer product, the polymerization mixture was added to 1000 ml of a methyl alcohol solution containing 0.74 g of phenyl-fl-naphthylamine and 7.5 g of an aqueous solution containing 30% by weight of sulfuric acid. The polymer product thus precipitated was washed with methyl alcohol and dried at room temperature. The dried polymer product was entirely in the form of powder. Table I shows the yield, reduced specific viscosity and the melting point of the polymer product as well as the content of l.2-structure in the polymer product. The microstructure oithe polymer product in Example 5 was determined by infrared absorption spectrum analysis using a KBr tablet method. The infrared absorption spectrum of the polymer product is indicated in FIG. 2. It was observed that the spectrum includes a remarkable absorption peak at 660 cm, which is characteristic of syndiotactic l,2-structure.

ln Comparison Example I. the same procedures as in Example I were repeated except that no methylalcohol was used. The results are indicated in Table I.

Table l Polymerization item mixture .Polymer product Amount of Content Melt- Reduced methyl ol l.2- ing specific alcohol structure point viscosity (milli- Yield ('16) (Cl ('0 sp/C) Example mole) ('1) Comparison Example I 0 63 99 195 0.95

I I0 72 99.2 I92 0.96 2 75 98.0 [89 0.94 3 l20 78 97.0 lti3 0.76 4 300 HS 95.4 173 0.82 5 500 97 93.6 I55 0.78 lixumple 6 700 82 92.6 l46 0.80 7 I000 l00 H94 I27 0.91 it i500 too this I23 0.x: 9 2500 K2 so ll5 0.99 it) 5000 50 85.5 ll0 l.06 ll toooo l6 84.7 l07 I05 EXAMPLES t: THROUGH 4| in each example. the same operations as in Example 5 were repeated except that the type ofalcohol as indi cated in Table 2 was used instead of methyl alcohol, The properties and yields olthe polymer products are indicated in Table 2.

Table 2 Polymerization item Mixture Polymer product Content Melt- Reduced Exof 1.2- ing specific ample Yield structure point 'll\l.\ ll No. Type or alcohol W l ('4 l (Cl in up! i ll Ethyl alcohol 73 9|.3 I 0.93 l3 n-Propyl alcohol 90 96.0 I74 14 n-Butyl alcohol 57 9l.5 I L02 l5 scc-Butyl alcohol 67 97.2 I84 0.96 l6 iso-llutyl alcohol 38 97.] 179 0.96 l7 Allyl alcohol 77 97.6 180 I8 Furt'uryl alcohol 52 97.2 "(7 l9 n-Amyl alcohol 79 95.5 174 0.89 20 sec-Amyl alcohol 52 99.0 I79 I03 2l iso-Amyl alcohol 75 92.0 I67 22 Grycerin 65 98.0 I89 0.89 23 Ethylene glycol 57 97.8 I88 LN) 24 Trtethylene glycol 89 90.2 I65 25 Propylene glycol 73 9L2 I84 0.89 26 l.3-Butane-diol l'l7 9L8 I65 0.97 27 l.6-Hexane-diol 83 98.4 I83 0.82 28 l.l0-Dccane-diol 51 95.4 185 0.63 29 Ethylene glycol mono-n-butyl ether l00 95.7 I58 0.80 30 Ethylene glycol monoethyl ether 72 96.0 l6l 3| l.l.l-trishydroxypropane 44 96.7 Hi6 32 l.2.6-hexane-triol 48 98.5 I89 33 Benzyl alcohol lilll 96.6 I77 085 34 Triphenyl Carbinol 50 94.3 159 35 n-Hcxan'ol 55 93.5 I75 36 2-Ethylbutyl 64 94.3 I76 alcohol 37 n-Heptyl alcohol 5| 95.2 I77 38 2-Octyl alcohol 79 95.7 l 39 2-Ethylhexyl 75 94.4 I78 alcohol 40 n-Decyl alcohol 5i 98.0 175 4l Lauryl alcohol 59 95.6 I69 EXAMPLE 42 AND COMPARISON EXAMPLE 2 The same operations as in Example 5 were repeated except that l millimole of cobalt acetylacetonate was used instead of cobalt octoate. The polymer product was obtained in a yield of 74% and had a melting point of l56C. a content of l,2--structure of 93.571 and a reduced specific viscosity of 0.73 nsp/C.

ln Comparison Example 2, the same operations as above were repeated using no methyl alcohol. The comparative polymer product was obtained in a yield of 6l .3% and had a melting point of lC, a content of l.2-structure of 98.8% and. a reduced specific viscosity of 0.85 nsp/C.

EXAMPLE 43 The same operations as in Example 5 were repeated except that cobalt octoate was used in an amount of 0.1 millimole instead of l millimole. The polymer product having a melting point of l59C and a content of 1.2- structure of 92.7% was obtained in a yield of 84% EXAMPLE 44 AND COMPARISON EXAMPLE 3 The same procedures as in Example 5 were repeated except that the polymerization was carried out at a temperature of 5 instead of 30C. The resultant polymer product was obtained in a yield of Sl'll and had a melting point of lft'l'f. a content of l.2-strttcture of 93.0 and a reduced specil'tc viscosity of 2.34 asp/T.

In Comparison Example 3. the same operations as above were repeated using no methyl alcohol. The comparative polymer product was obtained'in a yield of22.4Z and had a melting point of 203C. a content of I .Z-structure of 98.7% and a reduced specific viscosity Table 3 Item Polymerization Mixture (millimole) Polymer Product Catalyst Component Solution Example Content of Melting No. Methyl l.3- (.obalt 'l'riethyl Carbon Yield l.2-strueture point ttleohol btttttdlene ()ctottte aluminum dlttull'lde ('4 I ('4 I ((t 45 I25 2 0.25 0.5 (H5 .12 97.] I85 46 I25 0.25 0.5 ().IS 34 97.! I83 47 I [00 0.25 0.5 0.15 97.5 185 48 125 200 0.25 0.5 0.15 29 96.) I86 49 S00 2 l 2 0.6 I00 92.3 I57 of 2.1 nsp/C.

EXAMPLES THROUGH 49 In each of Examples 45 through 43. the following operations were carried out. In a 2.000 ml capacity glass separable flask from which the inside atmospheric air had been drawn out and replaced by nitrogen gas. 74 g of 1.3-butadiene was dissolved in 760 cc of dehydrated benzene. A portion of the benzene solution of 1.3- butadiene was withdrawn in the amount indicated in Table 3 from the 2.000 ml flask. and the withdrawn portion was mixed with about l0 ml of benzene receivcd in a I000 ml capacity glass separable flask in which the inside atmospheric air had been replaced by nitrogen gas. After the mixture was maintained in the EXAMPLES 50 THROUGH 54 In each example. the same operations as in Example 49 were carried out again except that a catalyst component solution was prepared in a 1.000 ml flask. using a portion of the benzene solution containing l.3- butadicne in an amount as indicated in Table 4. The catalyst component solution was mixed with 500 ml of methyl alcohol. and one minute after the mixing. the mixture was mixed with 0.6 millimoles of carbon disulfide which had been dissolved iin benzene in a concentration of 0.3 millimoles/ml. Finally. the mixture thus prepared was added to the remaining benzene solution of l,3-butadiene in the 2000 ml flask. The results are shown in Table 4.

Table 4 Item Polymerization Mixture lmillimole) Polymer Product Catalyst Component Solution Ex- Content of Melting ample l.3- Cobalt Tn'cthyl Methyl Carbon Yield l.2-structure point No. butadiene octoate aluminum alcohol disulftde (Z (Z I (C) 50 20 I 2 500 0.6 50 93.4 I62 51 I00 I 2 500 0.6 SI 93.l I62 52 200 I Z 500 0.6 62 9 l .9 I60 53 $00 I 2 500 0.6 82 92.4 I60 54 I000 I 2 500 0.6 82 93.3 I62 flask for one minute. 0.25 millimoles ofcobalt octoate EXAMPLE 55 in the state of a benzene solution containing 0.1 millimoles/ml of cobaltoctoate was added to the solution 50 in the 1.000 ml flask and. one minute after the above addition. 0.5 millimoles of triethylaluminum dissolved in benzene in a concentration of l millimoIe/ml. was added to the above mixture to prepare a catalyst component solution.

In order to prepare a polymerization mixture. I25 millimoles of methyl alcohol were added to the remaining solution in the 2.000 ml flask from which'a portion of the benzene solution had been withdrawn. and one minute after the above addition. the content of the L000 ml flask was mixed with the content ofthe2.000 ml flask and. one minute after the above mixing. 0.15 millimoles of carbon disulflde. which had been dis-. solved in benzene in a concentration of 0.3 millimoles/ml. were added to the mixture. The polymerization mixture was stirred at atemperature of 30C for minutes to polymerize l.3-butadiene. In order to isolate the polymer product. the polymerization mixture The same operations as in Example 49 were carried out again except that 500 millimoles of methyl alcohol, 0.6 millimoles of carbon disuli'tdc and a catalyst component solution containing 20 millimoles of l.3- butadiene were added. in the above-mentioned order. to the remaining benzene solution of I .3-butadiene in a 2.000 ml flask. A polymer product was obtained in yield of 88% and had a melting point of C and a contentvof l.2-structure of 88%.

COMPARISON EXAMPLES 4 THROUGH 8 referred to as "solution CS. were separately prepared and mixed in the order as indicated in Table at intervals of time of l minute to prepare a polymerization mixture. The polymerization mixture was agitated at a 14 acetylacetonate (Example 74) and cobalt dichloridedipyridine complex (Example 75 l. The results are indicated in Table 8.

Table 8 temperature of 30C for 60 minutes. In each compara- 5 tive example. no polymer product was obtained. R d d C UCL Content ol' Melting Specific Tdblc 5 Yield l.2-structure Point Viscosity Item Order of Mixing Catalyst Components P l PC) "WP 511m 1 1 4 5 to 74 47 91.4 h 0.7.1 limmpk. 75 so 9.1m to: 1.03 No.

2 2:: Ci Alcolhol I Al I CS C. A A coho Co a c. M c5, M EXAMPLES 76 AND 77 7 Al Alcohol ct cs, M 15 g c A] Alcuhm M In Example 76. the same procedures as in Example 59 were repeated except that the preparation ofa poly merization mixture was carried out by the following In the mixing orders as mentioned above. the catalyst mclhod- The in 2.000 ml apacity glass par l component solution was not prepared. This resulted in 5 W88 Sucked Out and t fl k was fi e with n ono production of polymer. gen gas. In the flask. 74 g of l.3-butadiene was dissolved in 760 ml of dehydrated benzene. A portion of EXAMPLES 56 THROUGH 6 AND COMPARISON the benzene solution containing 20 millimoles of l.3- EXAMPLE 9 butadiene was withdrawn from the 2.000 ml flask and In each example, the same operations as i Ex m l mixed with about l0 ml of benzene in a L000 ml cal were repeated except that ac ton i a q tit as i pacity glass flask from which the inside atmospheric air dicated in Table 6 was used instead of methyl alcohol. had n ra n out and replaced with nitrogen gas. The results are indicated in Table 6. The mixture-was maintained in the flask for l minute Table 6 Polymerization I Item mixture Content of Melting Reduced Specific Example Yield l.2-structure Point Viscosity No. Acetone tmillimole) (ll ('1) (T) (71 sp/C) st. l0 7] 90.3 :02 p 0.95 57 64 98.0 WI 0.98 5a r20 5x 96.ll- I83 0.85 59 500 93 93.6 I58 0.87 no I000 I00 89.5 I4I 0.RI at I500 I00 89.l r35 0.97 n: 2000 I00 88.0 NS L08 (.3 5000 I00 83.8 97 l.3l n4 toooo 75 82.7 86 0.97

EXAMPLES 65 THROUGH 73 In each example. the same operations as in Example 59 were repeated except that a type 'of ketone compound as indicated in Table 7 was used instead of acetone. The results are indicated in Table 7.

and. thereafter. mixed with I millimole of cobalt octoate which was in the state ofa benzene solution having a concentration of 0.1 mi'lIimoles/ml and. then. 2 millimoles of triethyl-aluminum which was in the state of a benzene solution ofa concentration of I milIimole/ml. at an interval of time of l minute. A catalyst compo- EXAMPLES 74 THROUGH '75 The same pro'cedures as in Example '59 were repeated twice using. in place of cobalt octoate. cobalt nent solution was obtained. Acetone in an amount of 500 millimoles was mixed with the remaining benzene solution of l.3-butadiene in the 2.000 ml flask and. at an interval of time of 1 minute. the above mixture was l'urther mixed with 0.6 millimoles olcarbon disullide in the state of a benzene solution having a carbon disulpolymer products of the examples had properties its indicatedin Table l I.

90 n-Dedecylaldehyde 50 fide concentration of 0.3 millimoles/ml..'l' he polymerization mixture thus prepared was stirred at aftemp'erature of 303C for60'minutes to allow l,3-butadieneto polymeriz eiz'lhe results'are indicated'in Table 91"? In Example77, the same procedure'as in Example 76 were'carried out again except that'the same catalyst component solution asin' Example.;76 was mixed with 500 millimoles of acetone and, at an interval of time of 1 m illimolesbt carbon disulfide at thestat e' of m le/ml concentration benzene solution to prepare'a catalysteompositiom and the eatalyst-com' position was added to the remaining benzene solution of l.3-butadiene inthe 2.000 ml flask, to prepare apatymerization mixture. The results are'shown in Table 9.

Table 9 Item Order of Mixing Polymer Product catalyst C(ll'flPOnt-lllli p t Content of 1 t l.2- Melting Ex- Yield structure Point ample I 2 3. 4. .(ill ('Z) (C)- 76 M Acetone (a cs, 8! 910 157 77 ;B Acetone CS, M 60 i t In the above table, M represents the remaining benzene solution of Lil-structure. B the catalyst component so-; lution and,CS the carbon disulfide;

i=.xit'ttit ei=.s 7 j anouloa 8 1T y In each examplegthe same operations as in Example 59 were repeated-except thatVp anisaIde'hyde-Lin an; f

amount as indicated in-Table I0 was used infplace or:

500 millimoles of' acetone. The results are shown in In Example 85, formaldehyde used was in the state of an aqueous solution containing 377: by weight of formaldehyde.

EXAMPLE 9| The same operations as in Example 76 were repeated except that 10.000 millimoles of cyclohexanone were used instead of S00 millimoles of acetone. A polymer "product was obtained in a yield oi 97'7:v and had a content of l.2-structure of 75.0% and a melting point of EXAMPLE 92 The same procedures as in Example 76 were repeated except that 5000 millimolesol p-anisaldehyde were used for 500 millimoles oi acetone. A polymer product was obtained in a yield of 407: and had a melting point of 94C.

EXAMPLES 93 THROUGH 96 In each example, the same procedures as in Example 56 were carried out except that the polymerization 'mixtulrel'was prepared the following method. 74 g of 1 l,3 '-bu tadiene was dissolved in 760 ml of dehydrated benzenereceived in a2. 000 ml capacity glass separable flask fromlwhich the'inside atmospheric air had been withdrawn and replaced by nitrogen gas. Into the solution prepared as stated above, triethylaluminum in the .state-ofia benzene solution oia concentration of l millimole'lmlwas added in an amount as indicated in Table 12;'

Thereafte r. atan interval of'timeo ll minute. I millimole of cobalt octoate. in the state of a benzene solution of a 0.l millimole/ml concentration. was added to Table the mixture toprepare a catalyst component solution.

1 Table IO l" l Polymerization: 1 i t l v y Item Mixture Polymer Product, t I. U t Contcnt'ol' Meltin'g' Reduced Specific. Example Amount of Yield l. 2-structurc Point I V ixcosityf s No. p-Anisaldehydc ('H (Ci) t.()' -(nsp/C)- 1s so 185 95.0 ms. ton 79 200 tot) 94.5 I39 0.95 so 500 100- 89.6 n L32 ill f 1000- too 855 95 .1.25 ttz .sxoo x 1 a s3 soon 30 mo 93 41.41 x4 r0000 2o i 78.0 so 1.31

. i l t One minute after completion of the preparation stated EXAMPLES THROUGH above. instead or It) millimo'les of acetone. s00 milli- In each example. the snme operations as in Example were-repeated usingfartypexol aldehyde compound asindicated in Tablell inplaee 'ol'p-anisal lehy'de.7he

moles of a ketone or aldehyde compound as indicated in 'lable'lZ'wcremixed-with the catalyst component .solutionand. at an interval of time of one minute. 0.6

17 millimoles ol'cttrbon disulfidc in the state ol'a benzene solution having a concentration of 0.3 millimoles/ml was added to the above mixture.

The resultant polymer products had the properties as minum were mixed to the solution. The mixture was maintained for 1 minute while stirring. The triethylaluminum charged above was in the state ofa benzene soindicated in Table I2. 5 lution co11taining(l.l millimole/ml oftriethylaluminum.

Table 12 item Polymerization Mixlure Polymer Product Amount of Content of Melting Reduced Specific l xantple 'lriethylaluminum Type of Ketone Yield III-structure Point YiSLusil) No. lmillimolet or Aldehyde' ("i (G l (Cl (mp/1'1 93 L0 Acetone 25 92 157 0.87 94 1.5 Acetone 77 92 157 0.112 95 L0 p-Anisultlehyde $4 92 I55 H7 90 1.5 p-Anisuldehyde I00 9| I50 L24 Thereafter. l millimolc of cobalt octoatc in the state of COMPARISON EXAMPLES 9 THROUGH 13 a benzene solution containing 0.1 millimole/ml of the In each comparison example. the same solution M. cobalt octoate was further mixed to the mixture in the Co.Al and CS as in Comparison Example4were sepa- 2.000 ml flask and. the mixture thus prepared was rately prepared and, then the solutionM. Co,'Al and stirred for l minute to provide a catalyst component CS and 500 millimoles otf acetone were mixed in the solution. Thereafter. methyl alcohol in an amount as sequence as indicated in Table 13, at intervals of time indicated in Table 14 was mixed with the catalyst comof l minute, to prepare a polymerization mixture. The ponent solution in the 2.000 ml flask and the mixture mixture was stirred at a temperature of 30C for 60 was stirred for l minute. 'At'terthat, 0.6 millimoles of minutes. It was observed that no polymer product was carbon disulflde in the state of a benzene solution conproduced. taining millimoles/ml of carbon disulflde. was Table charged'into the flask and the polymerization mixture thus prepared was stirred at a temperature of C for 1 Mixing 60 minutes to allow ll 3-butadiene to polymerize. Companson 30 Exam-pic p Thereafter. the polymenzatton m1xture was added to a l 2 3 5 l,000.ml of methyl alcohol solution containing 0.74 g 9 M Accumc of phenyl-B-naphthylamine and 7.5 g of a 30% sulfuric A 2 if" acid aqueous solution. to separate and deposit the poly- Memo v 'i' z M mcric product from the mixture. The polymeric prod- 13 Co Al Acetone j cs, M uetwas washed with methyl alcohol and dried at'room temperature. The dried polymer product was entirely 1 1 in the form of powder. Table 14 indicates the yields of l d h EXAMPLES 97 THROUGH 05 AND the po yrnertc pro uct content of 1 structure 1n t e COMPARISON EXAMPLE [5 40 polymcnc product as well as the melting po1nt and reduced specific viscosity of the polymeric product.

i i X Table l4 3 1 item 1 Amount of Yield of Content of Melting Reduced Specific 3 methyl alcohol polymer l.2-structure Point Viscosity Example added u u Non (millimolc) (X by weight) ("1) (C) lnsp/Cl .97 10 71 1 911.7 193 0.97 .911 40 74' 98.0 190 0.95 99 120 1 77 911.2 1115 0.110 100 500" 114 1 94.0 167 0.114

dures. ln :1 2,000 ml capacity glass scparableflask. from which the inside atmospheric airhad bcen'driawn out and replaced by nitrogen gas. 74 g of .Zl-buta dicnc was dissolved in 760 ml of dehydrated benzene containing EXAMPLES [06 THROUGH 122 Table I5 Item 1 Type of Alcohol Yield of Content of Melting Reduced Specific Example added polymer l .2-struc1urc Point Viscosity lllb' 1 Ethyl alcohol 75 g 88.6 l6) (NH 107 n-Propyl alcohol as 94.2 17: 0.112

ltlX n-l3utyl alcohol 55 90.8 l74 L00 Hi9 lnthhulyl alcohol 4| 94.6 no 0.97

item Type ol Alcohol Yield of Content of Melting Reduced Specific lzxample added polymer l.2-structurc Point Vi cosity No. 1'41 ('71) (C1 mp/Tl I I n-Amyl alcohol 77 94.8 I75 ".92 Ill n-Hexyl alcohol 5.1 92.4 172 0.83 I ll n-Hep1yl alcohol 48 94.) 177 0.84 H3 'l'oetyl alcohol ill 95.: [K2 0.8. U4 n-Dceyl alcohol 52 90.3 17-8 11 H0 H5 Lauryl alcohol hi 93.7 H 0.87 l lh Allyl alcohol 78 96.4 I79 t).l\'.'l ll7 Benzyl alcohol 84 94.8 175 0.114 H8 'l'rlphenyl carhlnol 53 93.8 Y 159 0.911 H9 Furluryl alcohol 51 96.7 1116 0.811 120 Triethylene glycol 85 89.5 166 1.08 lZl v LG-Hexane-diol 82 97.8 It 0.85 122 (.irycerinc 65 97.6 187 0.9l

EXAMPLE 1 23 AND COMPARISON EXAMPLE 16 The same operations as in Example I00 were repeated except that l millimole of cobalt acetylacetonate was used instead of cobalt octoate. The resultant polybutadiene had a yield of 72%, a content of 1.2- strueture of 92.7%. a melting point of 155C and a reduced specific viscosity of 0.78 nsp/C.

in Comparison Example 14. the same procedures as abovewere repeated except that no methyl alcohol was added. The resultant comparative polybutadiene had a yield of 58%, a content of l.2-polyb'utadicne of 99.l%, a melting point of 196C and a reduced specific viscosity of 0.83 asp/7C. t

EXAMPLES 124THROUGH 137 in each oijthe Ertamplcsil24 through 137. the same.

procedures as in Example 100 were carried out by using cobaltoctoate and triethylaluminum in amounts.

indicated in Table 16. The results are indicated in l.3-butadienc to dissolve the LB-butadiene. The henzene solution containing l,3-butadiene in the amount indicated in Table 17 was withdrawn from the 2.000 ml flask and mixed with approximately 10 ml of benzene contained in a L000 ml capacity glass separable flask. from which the inside atmospheric air had been withdrawn and replaced by nitrogen gas. and the solution was maintained in the flask for 1 minute. Thereafter. 3 millimoles ot'triethylaluminum in the state ofa benzene solution containing 1 millimole/ml oi' triethlaluminum was added to the 1.000 ml flask and one minute after the above addition. I millimole of cobalt octoate in the state of a benzene solution containing 0.1 millimoles/ml oi cobaltoctoate was added to the 1.000 ml The resultant liquid was a catalyst component solution. Thcremainder in the 2.000 ml flask was mixed, within the 2 ,000 ml flask. with 500 millim'oles of methyl alcohol. The mixture thus prepared was mixed with the catalyst component solution and one minute after completion of the mixing, 0.6 millimoles of carbon disulflde Table 16. 40 in the state of a benzene solution containing 0.3 mil- Table 16 Item Amount of Amount of Yield of Content of Melting Reduced cobalt octoate triethylpolybutadiene l.2-structure Point Specific added aluminum Viscosity Example added No. (millimole) (millimole) ('1) ('1) (C) ('qsp/Cl 124 6.0 3.0 311' 90.7 156 0.115 125 3.0 3.0 05 92.11 0.119 126 6.0 6.0 84 91.4 157 0.97 127 3.0 6.0 111 91.5 1511 0.95 1211 6.0 12.0 35 4 91.9 160 1.01 129 3.0 9.0 63 92.3 7 162 0.93 130 6.0 111.0 35 90.11 157 1.02 131 1.0 4.0 112 413.9 0.71: 132 3.0 12.0 511 a 91.7 1 162 '0.92 133 6.0- 24.0 35. 91.3 M62 0.911 134 0.2 2.0,. 50 92.2 159 0.94 1.35 0.1 v 2.0 20, -.91.11 .161 0.99 136 0.1 4.0 19 92.4 5161 1.02 137 6.0 Y 24.0 411' 94.1 163 1.15

EXAMPLES ISS THRO UGli 141.

in each olthe Examplesl38 through l4l. the follow; ing procedures were carried out. A 2.000 ml capacity glass separable l'lask. from which the inside atmospheric air hadbeen withdrawn and replaced by nitro- 5 gen gas was charged with 760 mlof dehydrated benzene (containing [.0 millimole of water) and 74 g of limolcs/ml otcarbon disttlfide were added to the mixture. The polymerization mixture thus prepared was stirred ut a temperature 0130C for 60 minutes to permit l.3-butadicne to polymerize. The resultant polybu- .tadiene was treated by the'same method as in Example I. Table I7 .indicates properties of the polybutadienes in the present examples.

Table 1? Catalyst component solution Amount of components Polymer ltem (millimolel l-Ixaml.3- Content of Melting ple huta- Triethyl- Cobalt Yield LZ-structure point No. dienc aluminum octoate ('1) ('1) (Cl I38 2 s l" 75 94.4 I63 l 39 20 3 l X 92.5

I I00 3 l 85 9L5 lol MI 200 3 l 87 92.7 I62 1 4.8 millimoles of water Corn arison Exam le l8). No EXAMPLES 142 THROUGH [46 I5 p p in each Example. the same operations as in Example I38 were carried out except that a catalyst component solution of a composition indicated in Table 18 was prepared. 500 millimoles of methyl alcohol were mixed with the catalyst component solution and, 1 minuteafter the above mixing. 0.6 millimoles of'carbon disulfide in the state of a benzene solution containing 0.3 millimoles/ml of carbon disultide-were added to the above mixture in order to prepare a catalyst composipolymer was produced in either of these comparison examples.

COMPARISON EXAMPLES 17 THROUGH 23 In each of the comparison Examples I? through 23. the same operations as in Example I00 were repeated using' triethylaluminum and cobalt octoate in amounts indicated in Table 19. The 760 ml dehydrated benzene contained 1 millimole of water.

Table I9 tron. The catalysteomposttion was mixed with the re- 25 mainder of the solution in the 2.000 ml flask.

' Comparison The results are m Tab]? Example No. Cobalt octoate Triethylaluminum Table I8 Catalyst component solution Amount of components Item (millimole) Polymer Hxaml.3- Content of Melting ple huta- Triethyl- Cobalt Yield l.2-strueture point No. dicne aluminum octoate ('4) (C4) (Cl 142 20 y 3 l 47 93.8 I64 I44 200 3 I II 92.6 I63 145 500 3 I so 9t.| I62 I46 1000 3 l 79 92.9 I64 The same operation as n Example 139 were repeated l i u except tllat 500 millimoles of methyl alcohol and 0.6 30 l 2 millimoles of carbon disulfide and a catalyst eompo- 81% g: .nent solution containing 20 millimoles of 1.3- 23 0.2 0.2;

butadiene. 3 millimoles oftriethylaluminumlan d 1 mil limole of cobalt octoate. were. separatcly'charged into the 2.000 ml flask containing the benzene solution of l.3'butadiene at an interval of time ofl minute.

A polymer product was obtained at a yield of 76% and had a melting point 0!- l52C and a content of L2- structure of 89.6%.

EXAMPLE I48 The same procedures as in Example lOO were re peated except that'760 cc of adehydrated benzene containing 0.4 millimoles of water was used. The poly-. mer product was obtained at a yield of'669i and had'a melting pointof 158C and a content of l.2-strueture of 90.4%..

COMPARISON EXAMPLES IS AND l6 The same operations as in Example 148 were repeated twice using 760 ml of adehydrated benzene containing 3.0 millimoles of water (Comparison Example l7) and 760 ml ota dehydrated benzene containing examples.

What we claim is:

l. A process for producing a butadiene polymer composed essentially of LZ-structure. comprising the steps of: I

A. preparing a catalyst component solution by dissolving, in an inert organic solvent containing l,3- butadienc. (a) at least one cobalt compound selectedlrom the group consisting of (i) B-diltetone complexes of cobalt. (ii) B-keto-aeid ester complexes'otcobalt. (iii) cobalt salts otorganic carboxylie acidshaving'o to IS carbon atoms. and (iv) complexes of halogenated cobalt compounds of the formula CoXn, wherein X represents a halogen atom'and'n represents 2 or 3. with an organic compound selected from the group consisting of tcr tiary amines alcohols. tertiary phosphines. ketones and N.N-dialkyl-amides. and (b) at least one or- 23 ganoalaminum compound of the formula AIR wherein R represents a ltydrocarbon radical ol 1 to 6 carbon atoms;

13. preparing a catalyst composition by mixing said catalyst component solution with (c) at least one organic compound selected from the group consisting 01' alcohol compounds having 1 to 25 carbon atoms. ketone compounds having 3 to 20 carbon atoms and aldehyde compounds having 1 to 20 carbon atoms and (d) carbon disulfidc:

C. providing a polymerization mixture containing desired amounts of 1.3-butadicne. said catalyst composition and an inert organic solvent. and;

D. polymerizing said 1.3-butadiene in said polymerization mixture at a temperature of -20 to 80C.

2. A process as claimed in claim 1. wherein said cata lyst component solution is prepared by firstly dissolving said cobalt compound into said inert organic solvent containing 1,3-butadiene and secondly dissolving said organoaluminum compound into the above solution.

3. A process as claimed in claim 1, wherein said catalyst compositioncontains 0.0005 to 1.0% by mole of said cobalt compound, 0.001 to 10% by moleof said organoaluminum compound, 0.510 5.000% by mole of said alcohol, ketone or aldehyde and 0.0005 to 2% by mole of said carbon disulfide. based on the amount by mole of said 1,3-butadiene in said polymerization mixture.

4. A process as claimed in claim 3, wherein said cobalt compound is in an amount of 0.001 to 0.5% by mole. said organoaluminum compound in 0.03 to 5% by mole. said alcohol, ketone or aldehyde in l to 1.000% by mole and said carbon disulfide in 0.001 to 1% by mole. based on the amount by mole of said 1.3- butadiene.

5. A process as claimed in claim 1, wherein said cata- 8. A process as claimed in claim 1, wherein the ratio by mole otthe amountoi said organoaluminum compound tosaid cobalt compound is in a range from 0.1 to 500.

9. A process as claimed in claim 8, wherein'said ratio by mole of the amount of said organoaluminum compound to said cobalt compound is from 0.5 to lOO. i 10. A process as claimed in claim 1, wherein said cat,

alyst composition is prepared at a temperature ofl 0 to 1,1. A process as claimed in claim 1, wherein the ratio by mole of the amount ofsaid alcohol. ketoneor aldehyde compound to said organoaluminum compound is in a range from 5 to 25,000. I a

12. A processas claimed in claim 11, wherein the ratio by mole of the amount olsaid alcohol. ketone or aldehyde compound to said organoaluminum compound is from 1010 5.000.. t

13. A process as claimed in claim 1, whereinsaid polymerization temperature is from 5 to 50C.

14. A process as claimed in claim I, whereinsaid 1.3- butadicne to be polymerized is in an amount of 2 to 24 30% based on said inert organic solvent in said polymerization mixture.

15. A process as claimed in claim 1. wherein said eatalyst composition further contains water in a ratio by mole ol'0.0l to 5.000 to the amount by mole oisaid cobalt compound.

16. A process as claimed in claim I. wherein said eatalyst component solution is prepared by lirstly dissolving said organoaluminum compound in said inert organic solvent containing 1.3-butadicne and secondly dissolving said cobalt compound in the above-prepared solution. and said catalyst component solution contains water. said organoaluminum compound and said cobalt compound in a ratio by mole percentage oia h c. said proportion a. h and c being on or within a figure dc fined. in a triangular coordinate system having three ordinates respectively presenting the mole percentages of said water. organoaluminum compound and cobalt compound. by coordinates A (a 49.8.!) 50 and c 0.2). B (a=0. b==99.8 and c=0.2).C (a=0. h=25 and c=).D(a=20.b=25 andc=55) and E (a=20. b =55 and c=25).

17. A process as claimed in claim 16, wherein said inert'organic solvent contains no or at most 500 ppm. of water based on the weight of said inert organic solvent.

18. A process as claimed in claim l7,whercin said amount of water is at most 200 ppm. based on the weight of said inert organicsolvient.

19. A process as claimed in claim 1, wherein said inert organic solvent is selected from the group consisting of aromatic hydrocarbons. aliphatic hydrocarbons. alicyclic hydrocarbons, halogenated aromatic hydrocarbons. halogenated aliphatic hydrocarbons. halogc' nated alicyclic hydrocarbons. and mixtures of two or more of the above-mentioned compounds.

20. A process aselaimed in claim 19, wherein said polymerization mixture further contains the same inert organic solvent as that used in said catalyst component solution.

21. A process as claimed in claim 1, wherein said B- diketone complex of cobalt has a diketone group of the formula:

wherein R'and R, which are the same as or different from one another. are each an alkyl radical of l to 6 carbon atoms and R'and R. which are the same as or different from one another, are each a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms.

22. A process as claimed in claim 1, wherein said [3- diketon'e complex of cobalt is either cobalt (ll) acetylacetonateor cobalt (111) acetylacetonate.

-23. A process as claimed in claim], wherein said B- keto-acid ester complex of cobalt has a B-kcto-acid ester group of the formula:

25 wherein R. R'-'. R and R are the same as defined above.

24. A process as claimed in claim I. wherein said B- keto-acid ester complex of cobalt is a cohalt-acctacctic acid ethyl ester complex.

25. A process as claimed in claim I. wherein said cohalt salt is either cobalt octoate or cobalt naphthcnate.

26. A process as claimed in claim I. wherein said complex of halogenated cobalt compound is either a complex of cobalt chloride with pyridine or ethyl alcohol.

27. A process as claimed in claim I. said organoaluminum compound ls selected from the group consisting of trimethylaluminum. triethylaluminum. tributylaluminum and triphenylaluminum.

28. A process as claimed in claim I. wherein said alcohol is selected from the group consisting of monohydric alcohols. polyhydric alcohols and polyhydric' alcohol derivatives having at least one hydroxyl radical.

29. A process as claimed in claim 28. wherein said monohydric alcohol is selected from the group consisting of saturated aliphatic alcohols. unsaturated aliphatic alcohols. alicyclic alcohols. aromatic alcohols and heterocyclic alcohols.

30. A process as claimed in claim 29, wherein said saturated aliphatic alcohol is selected from the group consisting of methyl alcohol. ethyl alcohol. n-propyl alcohol. isopropyl alcohol n-butyl alcohol. sec-butyl alcohol. tertbutyl alcohol, isobutyl alcohol. n-amyl alcohol. isoamyl alcohol. sec-amyl alcohol. tert-amyl alcohol. n-hexyl alcohol. 2-ethylbutyl alcohol. n-heptyl alcohol. 2-heptyl alcohol. n-octyl alcohol. 2-octyl alcohol. 2-cthylhexyl alcohol. capryl alcohol. nonyl alcohol. n-decyl alcohol. lauryl alcohol and 4- mcthylpentanol-2.

3]. A process as claimed in claim 29, wherein said unsaturated aliphatic alcohol is selected from the group consisting otallyl alcohol. crotyl alcohol and alcohol.

32. A process as claimed in claim 29, wherein said alicyclic alcohol is selected from the group consisting of cyclopentanol. cyclohexanol. Z-methylcyclohexanol and a-tcrpineol.

33. A process as claimed in claim 29, wherein said aromatic alcohol is selected from the group consisting of benzyl alcohol. cinnamyl alcohol and triphcnyl carbinol.

propargyl 34. A process as claimed in claim 29. wherein said.

26 liydroxypropanc. Lib-hexane triol. pcntacrythritol and trimethylol propane.

36. A process as claimed in claim 28. wherein said polyhydric alcohol derivative is selected from the group consisting of ethylene glycol monoalkyl ether. diethylcne glycol. diethylcne glycol monoalkyl ether. tricthylcnc glycol. triethylene glycol monoalkyl ether. propylene glycol monoalkyl ether and diacetonc alcohol.

37. A process as claimed in claim I. wherein said ketone compound is selected front the group consisting of aliphatic ketones. alicycliic ketoncs. aromatic ketoncs and heterocyclic ketones.

38. A process as claimed in claim 37. wherein said aliphatic ketone is selected from the group consisting of acetone. acetylacetone. ethylmethyl ketone. methylpropyl ketone. iso-propylmethyl ketone. butylmethyl ketone. isobutylmethyl ketone. pinacolone. diethyl kctone. butyronc. di-isopropyl ketone and di-isobutyl ketone.

39. A process as claimed in claim 37, wherein said alieyclic ketone is selected from the group consisting of cyclobutanone. cyclopentanone. cyclohexanone and cyclododecanone.

40. A process as claimed in claim 37, wherein said aromatic ketone is selected from the group consisting of acctophenone. propiophenone. butylophenone. valcrophenone. benzophenone. dibenzyl ketone and 2-aceto-naphthone.

41. A process as claimed in claim 39, wherein said hcterocyclic ketone is either 3-acetothienone or 2- acetoluron.

42. A process as claimed in claim 1, wherein said aldehyde compound is selected from the group consisting of aliphatic aldehydes. aliphatic dialdehydes. aromatic aldehydes. heterocyclic aldehydes.

43. A process as claimed in claim 42, wherein said aliphatic aldehyde is selected from the group consisting of formaldehyde.-acetaldehyde. propionaldehyde. nbutyl aldehyde. isobutyl aldehyde. n-valcraldehyde. isovaleraldehyde. pivalic aldehyde. caproic aldehyde. heptaldehyde. caprylic aldehyde. pelargonaldehyde. capric aldehyde. undecyl aldehyde. lauric aldehyde. tridecyl aldehyde. mystic aldehyde. pentadecylaldehyde. palmitic aldehyde and stearic aldehyde.

44. A process as claimed in claim 42, wherein said aliphatic dialdehyde is either glyoxal or succindialdehyde.

45..A process as claimed in claim 42. wherein said aromatic aldehyde is selected from the group consisting of benz aldchyde. omand p-tolualdehydes. salicyl aldehyde. aand B-naphthoaldehydes and o-. mand panisaldehydcs.

46. A process as claimed in claim 42. wherein said heterocyclic aldehyde is turtural.

l ll 4 I

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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
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Classifications
U.S. Classification526/93, 526/139, 526/142, 526/335, 526/141, 526/136
International ClassificationC08F136/06
Cooperative ClassificationC08F136/06
European ClassificationC08F136/06